Thin-film elemental analyses

Thin-Film Elemental Analyses for Precise Characterization of Minerals... 

With a known mineral, as determined by electron diffraction or other technique (such as X-ray diffraction), determination of the stoichiometry and structural formula can be a suitable test for analytical precision of thin-film elemental analyses. This simple test follows the practice commonly employed for electron microprobe data in which the accuracy (and completeness) of an analysis is judged by the departure from stoichiometry calculated for a given mineral. Thus, thin-film analyses of olivines, pyroxenes, garnets, feldspars and many other common rock-forming minerals can be examined for internal consistency via a calculation of structural formulae. 

Cation Site Distribution, Thin-film EDS analysis can also be used to quantitatively determine the site occupancy of atoms in a known crystal structure. Atom Location by Channeling Enhanced Microanalysis (ALCHEMI) is a technique which utilises electronchanneling enhanced X-ray emission for specific atoms in a crystal when appropriately oriented relative to the incident beam [43]. The method involves no adjustable parameters, can be used on relatively small areas of sample and provides fractional occupancies of atom positions [44] Unlike X-ray diffraction which has had limited success with adjacent elements in the periodic table [e.g. 45], ALCHEMI can provide site occupancies for adjacent elements and is relatively insensitive to sample thickness or the precise electron beam orientation [44] ... 

E282 Ratge, D., Kohse, K.P., Knoll, E. and Wisser, H. (1986). Evaluation of the multilayer technique using thin-film elements for analysis of electrolytes, substrates and enzymes. Poster presented at Gemeinsame Jahrestagung der Deutschen, Schweizerischen, Osterreichischen und Franzosischen Gesellschaft fiir Klinische Chemie, Basel, 22-25 October. 

XPS (X-ray Photoelectron Spectroscopy) or ESCA (Electron Spectroscopy for Chemical Analysis) as a surface analysis technique has been most widely used due to its high information content, flexibility in addressing a wide variety of samples, and sound theoretical basis since mid-1960s. Over the past few decades, XPS has been developed into the key snrface characterization method which combines surface sensitivity with the abihty to quantitatively obtain both elemental and chemical state information. Nowadays it is known that XPS is a very important analytical tool in the area of thin films. XPS analysis gives rise to useful information such as composition, chemical state, and thickness, etc., of thin film. 

The real utility of d comes in the analysis of thin films. Consider a substrate of refractive index supporting a thin film of thickness d and refractive index in contact with an internal reflection element (the prism) of refractive index as shown in Figure 24. In this case, d depends on the polarization of the incident light beam and is given by... 

Complete elemental analysis of complex thin-film structures to several pm depth, with excellent depth resolution... 

In the analysis of trace elements or thin films on substrate using electrons, however, one finds that the MDL, may be increased by choosing Eq such that Uis just greater than 1. The reason for this is that the k factor, which is the ratio of the intensity from the sample to that from the standard, increases as Uapproaches 1 for thin films. Thus, by maximizing the k factor, the sensitivity is increased. For bulk sample analysis, however, the k factor will usually be a maximum ax. U- 2.5. 

Interdiffusion of bilayered thin films also can be measured with XRD. The diffraction pattern initially consists of two peaks from the pure layers and after annealing, the diffracted intensity between these peaks grows because of interdiffusion of the layers. An analysis of this intensity yields the concentration profile, which enables a calculation of diffusion coefficients, and diffusion coefficients cm /s are readily measured. With the use of multilayered specimens, extremely small diffusion coefficients (-10 cm /s) can be measured with XRD. Alternative methods of measuring concentration profiles and diffusion coefficients include depth profiling (which suffers from artifacts), RBS (which can not resolve adjacent elements in the periodic table), and radiotracer methods (which are difficult). For XRD (except for multilayered specimens), there must be a unique relationship between composition and the d-spacings in the initial films and any solid solutions or compounds that form this permits calculation of the compo-... 

Since the 1950s XRF has been used extensively for the analysis of solids, powders, and liquids. The technique was extended to analyze thin-film materials in the 1970s. XRF can be used routinely for the simultaneous determination of elemental composition and thickness of thin films. The technique is nondesuuctive, rapid, precise, and potentially very accurate. The results are in good agreement with other elemental analysis techniques including wet chemical, electron-beam excitation techniques, etc. 

In addition to qualitative identification of the elements present, XRF can be used to determine quantitative elemental compositions and layer thicknesses of thin films. In quantitative analysis the observed intensities must be corrected for various factors, including the spectral intensity distribution of the incident X rays, fluorescent yields, matrix enhancements and absorptions, etc. Two general methods used for making these corrections are the empirical parameters method and the fimdamen-tal parameters methods. 

In multiple-layer thin films, it is possible that some of the elements may be present simultaneously in two or more layers. XRF analysis of this type of film can be complicated and cannot be made solely from their observed intensities. Additional information, such as the compositions or thickness of some of the layers is needed. The amount of addidonal non-XRF information required depends on the complexity of the film. For example, in the analysis of a FeMn/NiFe double-layer film, the additional information needed can be the composition or thickness of either the FeMn or NiFe layer. Using the composition or thickness of one of the film predetermined from a single-layer film deposited under identical condidons, XRF analysis of the FeMn/NiFe film was successfiil. ... 

Both XRF and EPMA are used for elemental analysis of thin films. XRF uses a nonfocusing X-ray source, while EPMA uses a focusing electron beam to generate fluorescent X rays. XRF gives information over a large area, up to cm in diameter, while EPMA samples small spots, (om in size. An important use of EPMA is in point-to-point analysis of elemental distribution. Microanalysis on a sub- lm scale can be done with electron microscopes. The penetration depth for an X-ray beam is normally in the 10-(om range, while it is around 1 (om for an electron beam. There is, therefore, also a difference in the depth of material analyzed by XRF and EPMA... 

If the secondary ion component is indeed negligible, the measured SNMS ion currents will depend only on the ionizing mode, on the atomic properties of the sputtered atoms, and on the composition of the sputtered sample. Matrix characteristics will have no effect on the relative ion currents. SNMS analysis also provides essentially complete coverage, with almost all elements measured with equal facility. All elements in a chemically complex sample or thin-film structure will be measured, with no incompleteness due to insensitivity to an important constituent element. Properly implemented SNMS promises to be a near-universal analytical method for solids analysis. 

Approximately 70 different elements are routinely determined using ICP-OES. Detection limits are typically in the sub-part-per-billion (sub-ppb) to 0.1 part-per-million (ppm) range. ICP-OES is most commonly used for bulk analysis of liquid samples or solids dissolved in liquids. Special sample introduction techniques, such as spark discharge or laser ablation, allow the analysis of surfaces or thin films. Each element emits a characteristic spectrum in the ultraviolet and visible region. The light intensity at one of the characteristic wavelengths is proportional to the concentration of that element in the sample. 

An EDX spectrum typical of thin-film analysis in TEM/(S)TEM is shown in Eig. 4.26. It was obtained from a polycrystalline TiC/Zr02 ceramic by use of an Si(Li) detector at 100 keV primary electron energy. Eor spectrum recording the electron probe of approximately 1 nm in diameter was focused on the triple junction between the grains in the STEM mode (Eig. 4.26a). Besides the elements expected for the material under investigation, viz. Ti and Zr, Si, Ee, and Co were also detected, hinting at the presence of a (Ee, Co) silicide as an impurity. Eor ceramic materials it is known that... 

Unfortunately, only thin films of about 20 nanometers in thickness could be obtained with Gel4 An ex situ analysis was difficult, because of experimental limitations, but XPS clearly showed that elemental Ge was also obtained, besides... 

PicArsn FRL Res Engr Lgbk 761-146 (1973) 56) S.I. Morrow, Microscopical Combustion Studies of Nitrocellulose Thin Films in Pres surized Capillary Tubes , Microscope 22, 229— 241 (1973) 57) Anon, Element Analysis of... 

State-of-the-art TOF-SIMS instruments feature surface sensitivities well below one ppm of a mono layer, mass resolutions well above 10,000, mass accuracies in the ppm range, and lateral and depth resolutions below 100 nm and 1 nm, respectively. They can be applied to a wide variety of materials, all kinds of sample geometries, and to both conductors and insulators without requiring any sample preparation or pretreatment. TOF-SIMS combines high lateral and depth resolution with the extreme sensitivity and variety of information supplied by mass spectrometry (all elements, isotopes, molecules). This combination makes TOF-SIMS a unique technique for surface and thin film analysis, supplying information which is inaccessible by any other surface analytical technique, for example EDX, AES, or XPS. 

XPS is among the most frequently used techniques in catalysis. It yields information on the elemental composition, the oxidation state of the elements and, in favorable cases, on the dispersion of one phase over another [ J.W. Niemantsverdriet, Spectroscopy in Catalysis, An Introduction (2000), Wiley-VCH, Weinheim G. Ertl and J. Kiippers, Low Energy Electrons and Surface Chemistry (1985), VCH, Weinheim L.C. Feldman and J.W. Mayer, Fundamentals of Surface and Thin Film Analysis (1986), North-Holland, Amsterdam]. 

The primary consideration for all AEM analysis is that the specimen be thin (generally carbon coated electron microscope grid either dry or in a suitable liquid. If a liquid suspension is used in preparing the specimen, it is important that all elements of interest are insoluble in that liquid. Only particles thin enough to meet AEM thin-film criteria (15) should be analyzed quantitatively. Scraping surface particles from a catalyst pellet for specimen preparation may be more useful than grinding the entire pellet. 

Polymer/additive analysis then usually proceeds by separation of polymer and additives (cf. Scheme 2.12) using one out of many solvent extraction techniques (cf. Chapter 3). After extraction the residue is pressed into a thin film to verify that all extractables have been removed. UV spectroscopy is used for verification of the presence of components with a chromophoric moiety (phenolic antioxidants and/or UV absorbers) and IR spectroscopy to verify the absence of IR bands extraneous to the polymer. The XRF results before and after extraction are compared, especially when the elemental analysis does not comply with the preliminary indications of the nature of the additive package. This may occur for example in PA6/PA6.6 blends where... 

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